Catalytic composition and olefin disproportion process

Abstract

The invention concerns a catalytic composition for olefin disproportion (also known as metathesis) produced by dissolving a tungsten and/or molybdenum compound, more particularly a tungsten and/or molybdenum halide substituted with one or more phenoxo groups containing at least two hydrocarbon substituents in the ortho, ortho' positions, in a medium produced by mixing at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide, at least one aluminum halide, and an organometallic aluminum compound. The invention also concerns an olefin disproportion process using this composition.

We claim: 
     
       1. A catalytic composition comprising at least one tungsten or molybdenum compound which is at least partially dissolved in a non aqueous ionic medium produced by bringing into contact: (A) at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide; (B) at least one aluminum halide; and (C) at least one organometallic aluminum compound of the formula AlR x  X 3-x  wherein R is a linear or branched alkyl radical containing 2 to 8 carbon atoms, X is chlorine or bromine and x equals 1, 2 or 3. 
     
     
       2. A catalytic composition according to claim 1, wherein (A) comprises N-butylpyridinium chloride, ethylpyridinium bromide, 3-butyl-1-methyl imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride or trimethylphenyl ammonium chloride. 
     
     
       3. A catalytic composition according to claim 1 wherein (A) comprises tetrabutylphosphonium chloride. 
     
     
       4. A catalytic composition according to claim 1, wherein the aluminium halide is aluminium chloride or aluminium bromide. 
     
     
       5. A catalytic composition according to claim 1, wherein the organic aluminium compound dichloroethylaluminium, dichloroisobutyaluminium, chlorodiethylaluminium, ethylaluminium sesquichloride or isobutylaluminium sesquichloride. 
     
     
       6. A catalytic composition according to claim 1, wherein the molar ratio A:B is between 1:0.5 and 1:3, and the molar ratio B:C is between 1:0.01 and 1:1.5. 
     
     
       7. A catalytic composition according to claim 1, wherein the molar ratio A:B is between 1:0.8 and 1:2 and the molar ratio B:C is between 1:0.1 and 1:1. 
     
     
       8. A catalytic composition according to claim 1, wherein the tungsten compound has the general formula WX 6-x  (OAr) x , where X represents chlorine or bromine and Ar represents an aromatic group containing at least two hydrocarbon substituents in the ortho, ortho' positions, and x equals 1 or 2. 
     
     
       9. A catalytic composition according to claim 1, wherein the molybdenum compound has the general formula MoX 5-x  (OAr) x , where X represents chlorine or bromine and Ar represents an aromatic group containing at least two hydrocarbon substituents in the ortho, ortho' positions, and x equals 1 or 2. 
     
     
       10. A catalytic composition according to claim 1, wherein (A) comprises N-butylpyridinium chloride, ethylpyridinium bromide, 3-butyl-1-methyl imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride, trimethylphenyl ammonium chloride, or tetrabutylphosphonium chloride. 
     
     
       11. A catalytic composition according to claim 10; wherein the tungsten compound has the general formula WX 6-x  (OAr) x , wherein X represents chlorine or bromine and Ar represents an aromatic group containing at least two hydrocarbon substituents in the ortho, ortho' positions, and x equals 1 or 2. 
     
     
       12. A catalytic composition according to claim 10, wherein the molybdenum compound has the general formula MoX 5-x  (OAr) x , wherein X represents chlorine or bromine and Ar represents an aromatic. 
     
     
       13. A catalytic composition according to claim 11, wherein the molar ratio A:B is between 1:0.5 and 1:3, and the molar ratio B:C is between 1:0.01 and 1:1.5. 
     
     
       14. A catalytic composition according to claim 11, wherein the molar ratio A:B is between 1:0.8 and 1:2 and the molar ratio B:C is between 1:0.1 and 1:1. 
     
     
       15. A catalytic composition according to claim 12, wherein the molar ratio A:B is between 1:0.5 and 1:3, and the molar ratio B:C is between 1:0.01 and 1:1.5. 
     
     
       16. A catalytic composition according to claim 12, wherein the molar ratio A:B is between 1:0.8 and 1:2 and the molar ratio B:C is between 1:0.1 and 1:1. 
     
     
       17. A catalytic composition according to claim 13, wherein the tungsten compound is WCl 4  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] 2 , WCl 4  [O-2,4,6-C 6  H 2  (C 6  H 5 ) 3  ] 2 , WCl 5  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] or WCl 4  [O-2,6-C 6  H 3  (C 4  H 9 ) 2  ] 2 . 
     
     
       18. A catalytic composition according to claim 14, wherein the tungsten compound is WCl 4  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] 2 , WCl 4  [O-2,4,6-C 6  H 2  (C 6  H 5 ) 3  ] 2 , WCl 5  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] or WCl 4  [O-2,6-C 6  H 3  (C 4  H 9 ) 2  ] 2 . 
     
     
       19. A composition according to claim 15, wherein the molybdenum compound is MoCl 3  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] 2 . 
     
     
       20. A composition according to claim 16, wherein the molybdenum compound is MoCl 3  [O-2,6-C 6  H 3  (C 6  H 5 ) 2  ] 2 .